RS51689B - SYNERGETIC HERBICIDE PROCEDURES AND MIXTURES - Google Patents

SYNERGETIC HERBICIDE PROCEDURES AND MIXTURES

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Publication number
RS51689B
RS51689B YU27402A YUP27402A RS51689B RS 51689 B RS51689 B RS 51689B YU 27402 A YU27402 A YU 27402A YU P27402 A YUP27402 A YU P27402A RS 51689 B RS51689 B RS 51689B
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group
ethyl
alkyl
formula
herbicide
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YU27402A
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Serbian (sr)
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Ronald Steven Pidskalny
Roy Allan Killins
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Basf Aktiengesellschaft
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Publication of YU27402A publication Critical patent/YU27402A/en
Publication of RS51689B publication Critical patent/RS51689B/en

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Catching Or Destruction (AREA)

Abstract

Sinergetska herbicidna kompozicija naznačena time što sadrži poljoprivredno prihvatljiv nosač i sinergetski efikasnu količinu smeše dva herbicida, kombinaciju ariloksipikolinamida formule IgdeZ predstavlja kiseonik ili atom sumpora;R1 predstavlja vodonik ili atom halogena ili alkil ili haloalkil grupu;R2 predstavlja vodonik ili alkil grupu; q je 0 ili1;R3 predstavlja vodonik ili alkil ili alkenil grupu;ili svaka grupa X nezavisno predstavlja atom halogena ili opciono supstituisanu alkil ili alkoksi grupu, poželjno haloalkil grupu, ili alkeniloksi, cijano, karboksi, alkoksi-karbonil, (alkiltio)karbonil, alkilkarbonil, amido, alkilamido, nitro, alkiltio, haloalkiltio, alkeniltio, alkiniltio, alkil-sulfinil, alkilsulfonil, alkiloksiaminoalkil ili alkeniloks-iminoalkil grupu;n je 0 ili ceo broj od 1 do 5;ili svaka grupa Y nezavisno predstavlja atom halogena ili alkil, nitro, cijano, haloalkil, alkoksi ili haloalkoksi grupu; im je 0 ili ceo broj od 1 do 5ili jednu od kompatibilnih soli jedinjenja formule I koje ne zagađuju životnu sredinu;i drugi herbicid koji je ariloksifenoksipropionat herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom.Prijava sadrži još 10 patentnih zahteva.A synergistic herbicidal composition comprising an agriculturally acceptable carrier and a synergistically effective amount of a mixture of two herbicides, the aryloxypicolinamide combination of formula IgdeZ represents oxygen or a sulfur atom, R1 represents a hydrogen or halogen atom or an alkyl or haloalkyl group, R2 represents hydrogen or an alkyl group; q is 0 or 1, R 3 represents hydrogen or an alkyl or alkenyl group, or each group X independently represents a halogen atom or an optionally substituted alkyl or alkoxy group, preferably a haloalkyl group, or an alkenyloxy, cyano, carboxy, alkoxycarbonyl, (alkylthio) carbonyl, alkylcarbonyl, amido, alkylamido, nitro, alkylthio, haloalkylthio, alkenylthio, alkynylthio, alkylsulfinyl, alkylsulfonyl, alkyloxyaminoalkyl or alkenyloxy-iminoalkyl group, n is 0 or an integer from 1 to 5, or each group Y independently represents an alkyl atom ha , a nitro, cyano, haloalkyl, alkoxy or haloalkoxy group; im is 0 or an integer from 1 to 5 or one of the compatible salts of the compounds of formula I which do not pollute the environment, and another herbicide which is an aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, phenoxaprop-ethyl, phenoxaprop-p -ethyl, hizalofop-p-terfuryl, hizalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, phentioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its intermediate salts or The application contains 10 more patent claims.

Description

Ariloksipikolinamidi kao što su oni koji su opisani u U.S. 5,294,597 pokazuju izvrsnu herbicidnu aktivnost, posebno za kontrolu-suzbijanje širokolisnih korova u žitnim usevima. Medjutim, pomenuti ariloksipikolinamidi, kada se upotrebe kao jedini aktivni sastojak, ne postižu zauvek uspešnu kontrolu potpunog spektra korova u pitanju koja se zahteva u komercijalnoj poljoprivrednoj praksi u primenjenim količinama koje su potrebne za prihvatljivu bezbednost useva. Takav nedostatak u spektru kontrole često se ne može dopustiti pri ko-tretiranju sa drugim herbicidom koji je efikasan naspram relevantnih vrsta korova. Izneto je u (U.S. 5,674,807) da odabrane kombinacije ariloksipikolinamida proizvode ne samo očekivani dodatni efekat, već mogu da ispolje značajan sinergetski efekat (naime, kobinacija pokazuje mnogi viši nivooaktivnosti nego onaj koji se predvidja od onog za pojedinačne komponente). Ovaj sinergetski efekat omogućava veću marginu bezbednosti za vrste useva. Aryloxypicolinamides such as those described in U.S. Pat. 5,294,597 show excellent herbicidal activity, especially for the control-suppression of broadleaf weeds in cereal crops. However, said aryloxypicolinamides, when used as the sole active ingredient, do not always achieve successful control of the full spectrum of weeds in question required in commercial agricultural practice in applied amounts required for acceptable crop safety. Such a lack of control spectrum often cannot be tolerated when co-treating with another herbicide that is effective against the relevant weed species. It is reported in (U.S. 5,674,807) that selected combinations of aryloxypicolinamides produce not only the expected additive effect, but can exhibit a significant synergistic effect (namely, the combination exhibits much higher levels of activity than that predicted from the individual components). This synergistic effect allows a greater margin of safety for crop types.

Prema tome, cilj ovog pronalaska je da se obezbede sinergetske, selektivne herbicidne kombinacije za useve sa širokim spektrom kontrole korova. Accordingly, it is an object of the present invention to provide synergistic, selective herbicidal combinations for crops with broad spectrum weed control.

Sledeći cilj ovog pronalaska je da se obezbede herbicidne smeše korisne za sinergetsku kontrolu širokog spektra korova u prisustvu useva. A further object of the present invention is to provide herbicidal compositions useful for the synergistic control of a wide range of weeds in the presence of crops.

Mada ariloksipikolinamidi kao jedinjenja pokazuju izvrsnu herbicidnu aktivnost, kada se primene kao jedini aktivan sastojak, ista ne pokazuju zauvek uspešnu kontrolu potpunog spektra korova u pitanju u količinama koje se zahtevaju za prih-vatijivu bezbednost useva. Neočekivano, nadjeno je da kombinacija sa dva herbicida koja sadrži ariloksipikolinamid jedinjenje formule I Although the aryloxypicolinamides as compounds show excellent herbicidal activity, when applied as the sole active ingredient, they do not always show successful control of the full spectrum of weeds in question in the amounts required for acceptable crop safety. Unexpectedly, it was found that a combination with two herbicides containing an aryloxypicolinamide compound of formula I

gde where

Z predstavlja kiseonik ili atom sumpora; Z represents oxygen or a sulfur atom;

Ripredstavlja vodonik ili atom halogena ili alkil ili haloalkil grupu; Represents hydrogen or a halogen atom or an alkyl or haloalkyl group;

R2predstavlja vodonik ili alkil grupu; R2 represents hydrogen or an alkyl group;

q je 0 ili 1; q is 0 or 1;

R3predstavlja vodonik ili alkil ili alkenil grupu; ili svaka grupa X nezavisno predstavlja R3 represents hydrogen or an alkyl or alkenyl group; or each group X independently represents

atom halogena ili opciono supstituisanu alkil ili alkoksi grupu; poželjno haloalkil grupu, ili alkeniloksi, cijano, karboksi, alkoksikarbonil, (alkiltio)karbonil, alkilkarbonil, amido, alkilamido, nitro, alkiltio, haloalkiltio, alkeniltio, alkiniltio, alkilsulfinil, alkilsulfonil, alkiloksiminoalkil ili alkeniloksimino-alkil grupu; a halogen atom or an optionally substituted alkyl or alkoxy group; preferably a haloalkyl group, or an alkenyloxy, cyano, carboxy, alkoxycarbonyl, (alkylthio)carbonyl, alkylcarbonyl, amido, alkylamido, nitro, alkylthio, haloalkylthio, alkenylthio, alkynylthio, alkylsulfinyl, alkylsulfonyl, alkyloximinoalkyl or alkenyloximino-alkyl group;

n je 0 ili ceo broj od 1 do 5; n is 0 or an integer from 1 to 5;

ili svaka grupa Y nezavisno predstavlja atom halogena ili alkil, nitro, cijano, haloalkil, alkoksi ili halo-alkoksi grupu; i or each group Y independently represents a halogen atom or an alkyl, nitro, cyano, haloalkyl, alkoxy or halo-alkoxy group; and

m je 0 ili ceo broj od 1 do 5; m is 0 or an integer from 1 to 5;

ili jedna od kompatabilnih soli jedinjenja formule I koje ne zagadjuju životnu sredinu; or one of the compatible salts of the compounds of formula I which do not pollute the environment;

plus drugi herbicid koji je ariloksifenoksipropionat plus another herbicide which is aryloxyphenoxypropionate

herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom, kao herbicida pokazuju sinergetski herbicini efekat. Takodje, neočekivano, odabrana kombinacija sa tri herbicida koja sadrži ariloksipikolinamid jedinjenje formule I i drugi herbicid koji je ariloksifenoksipropionska kiselina - herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom i treći herbicid koji je 2,4-D ili jedan od njenih kompatabilnih estara ili soli, ostvaruje značajan sinergetski efekat. Tako, povoljno, sinergetske kombinacije sa dva i tri herbicida prema ovom pronalasku dopuštaju niže aplikacione količine pomenutog ariloksipikolinamida pored povećanog spektra kontrole korova. Štaviše, sinergetski herbicidni postupci i smeše prema ovom pronalasku ostvaruju znatne povoljnosti u pogledu efektivne rezistentnosti. a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hyzalofop-ethyl and hyzalofop-p-ethyl or one of its environmentally compatible salts or esters, as herbicides, they show a synergistic herbicidal effect. Also, unexpectedly, a selected three-herbicide combination comprising an aryloxypicolinamide compound of formula I and another herbicide which is an aryloxyphenoxypropionic acid - a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters and a third herbicide which is 2,4-D or one of its compatible esters or salts, achieves a significant synergistic effect. Thus, advantageously, synergistic two- and three-herbicide combinations according to the present invention allow lower application rates of said aryloxypicolinamide in addition to increased spectrum of weed control. Moreover, the synergistic herbicidal methods and compositions of the present invention achieve significant advantages in terms of effective resistance.

Ovaj pronalazak obezbedjuje postupak za sinergetsku kontrolu neželjenih biljaka kao što su Polvgonum, Kochia, Galeopsis, Galium, Stelaria, Sinapis, i Avena koji obuhvata primenu na mesta na kojima rastu pomenute biljke ili na lišće ili korene pomenutih biljaka sineregetski efikasnu količinu kombinacije sa dva herbicida, koja sadrži ariloksipikolinamid jedinjenje formule I plus drugi herbicid koji je ariloksifenoksipropionat herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom. Ovaj pronalazak takodje obezbedjuje postupak za sinergetsku kontrolu neželjenih biljaka koja obuhvata primenu na mesta na koji rastu pomenute biljke sineregetski efikasne količine kombinacije sa tri herbicida koja obuhvata ariloksipikolinamid jedinjenje formule I, drugi herbicid koji je ariloksifenoksipropionska kiselina - herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom i treći herbicid koji je 2,4-D ili jedan od njenih kompatabilnih estara ili soli. The present invention provides a method for the synergistic control of undesirable plants such as Polvgonum, Kochia, Galeopsis, Galium, Stelaria, Sinapis, and Avena which comprises applying to the growing sites of said plants or to the leaves or roots of said plants a synergistically effective amount of a two-herbicide combination comprising an aryloxypicolinamide compound of formula I plus another herbicide which is an aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, phenthioprop, propahizafop, hyzalofop-ethyl and hyzalofop-p-ethyl or one of its environmentally compatible salts or esters. The present invention also provides a method for synergistic control of unwanted plants comprising applying to the sites where said plants grow a synergistically effective amount of a three-herbicide combination comprising an aryloxypicolinamide compound of formula I, the second herbicide being aryloxyphenoxypropionic acid - a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hizalofop-p-terfuryl, hizalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, phenthioprop, propahizafop, hyzalafop-ethyl and hyzalafop-p-ethyl or one of its environmentally compatible salts or esters and a third herbicide that is 2,4-D or one of its compatible esters or salts.

Ovaj pronalazak takodje obezbedjuje sineregetsku herbicidnu smešu koja sadrži poljoprivredno prihvatljiv nosač i sinergetski efikasnu količinu kombinacije sa dve herbicida od ariloksipikolinamida jedinjenja formule I plus drugi herbicid koji je ariloksifenoksipropionat herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom; ili obezbedjuje kombinaciju sa tri herbicida od ariloksipikolinamida jedinjenja formule I, drugog herbicida koji je ariloksifenoksipropionska kiselina - herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom i trećeg herbicida koji je 2,4-D ili jedan od njenih kompatabilnih estara ili soli. The present invention also provides a synergetic herbicidal composition comprising an agriculturally acceptable carrier and a synergistically effective amount of a combination of two aryloxypicolinamide herbicides of the compound of formula I plus another herbicide which is an aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, phenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters; or provides a combination with three herbicides of aryloxypicolinamide compounds of formula I, the second herbicide being aryloxyphenoxypropionic acid - a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters and a third herbicide which is 2,4-D or one of its compatible esters or salts.

Ariloksipikolonamidi formule I Aryloxypicolonamides of formula I

gde Z, Ri, R2, R3, X, n, i m su kao što je ovde gore definisano, a postupci za njihovo dobijanje su opisani u U.S. 5,294,597. Pomenuti ariloksipikolinamidi pokazuju izvrsnu herbicidnu aktivnost, posebno za kontrolu širokolisnih korova u žitnim usevima. Medjutim, kada se pomenuti ariloksipikolinamidi upotrebe kao jedini aktivan sastojak, ne postiže se zauvek uspešna kontrola potpunog spektra korova u pitanju koja se zahteva u komercijalnoj poljoprivrednoj praksi, a u vezi sa pouzdanom selektivnošću za žitne useve. where Z, R 1 , R 2 , R 3 , X, n, and m are as defined herein above, and procedures for their preparation are described in U.S. Pat. 5,294,597. The mentioned aryloxypicolinamides show excellent herbicidal activity, especially for the control of broadleaf weeds in cereal crops. However, when the mentioned aryloxypicolinamides are used as the only active ingredient, the successful control of the full spectrum of weeds in question, which is required in commercial agricultural practice, and in connection with reliable selectivity for cereal crops, is not always achieved.

Neočekivano, sada je utvrdjeno da kombinacija sa dva herbicida od ariloksipikolinamida formule I i drugog herbicida odabranog od ariloksifenoksipropionat herbicida koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom, obezbedjuje sineregetsku kontrolu za zabrinjavajuće korove kao što su Polvgonum, Kochia, Galeopsis, Galium, Stelaria, Sinapis, i Avena. Takodje, neočekivano, kombinacija sa tri herbicida i to ariloksipikolin-amida formule I i drugog herbicida koji je ariloksifenoksipropionska kiselina - herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom i trećeg herbicida koji je 2,4-D ili jedan od njenih kompatabilnih estara ili soli, obezbedjuje sinergetsku kontrolu korova. Tako, primena kombinacija sa dva ili sa tri herbicida prema ovom pronalasku ostvaruje obostrano pojačano dejstvo tako da se primenjene količine pojedinačnih herbicidnih komponenti mogu redukovati, pa se ipak isti herbicidini efekat postiže ili, alternativno, primena kombinacije herbicidnih komponenti pokazuje veći herbicidni efekat od očekivanog od efekta kod primene pojedinačnih herbicidnih komponenti kada se primena pojedi-načno u količina koje su prisutne u kombinaciji (sineregetski efekat). Unexpectedly, it has now been found that a combination of two aryloxypicolinamide herbicides of formula I and another herbicide selected from an aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop-butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters, provides synergetic control for weeds of concern such as Polvgonum, Kochia, Galeopsis, Galium, Stelaria, Sinapis, and Avena. Also, unexpectedly, a combination with three herbicides namely aryloxypicolin-amide of formula I and another herbicide which is aryloxyphenoxypropionic acid - a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters and a third herbicide which is 2,4-D or one of its compatible esters or salts, provides synergistic weed control. Thus, the application of combinations with two or three herbicides according to this invention achieves a mutually enhanced effect so that the applied amounts of individual herbicide components can be reduced, and yet the same herbicidal effect is achieved or, alternatively, the application of a combination of herbicide components shows a greater herbicidal effect than expected from the effect of the application of individual herbicide components when applied individually in the amounts that are present in the combination (synergetic effect).

Ariloksipikolinamidi formule I mogu da egzistiraju u obliku njihovih kompatabilnih soli koje ne zagadjuju životnu sredinu. Prikladne soli su, generalno, soli onih katjona, ili adicione soli sa kiselinama, koji katjoni odnosno anjoni nemaju štetno delovanje u pogledu herbicidnog dejstva aktivnih sastoj aka. Aryloxypicolinamides of formula I can exist in the form of their compatible salts which do not pollute the environment. Suitable salts are, in general, salts of those cations, or addition salts with acids, which cations or anions do not have a harmful effect in terms of the herbicidal effect of the active ingredients.

Odgovarajući katjoni su, osobito, joni alkalnih metala, radije litijum, natrijum i kalijum, zemnoalkalnih metala, radije kalcijum i magnezij um, i tranzicioni, metali, radije mangan, bakar, cink i gvoždje, a takodje i amonijum, pri čemu je moguće u ovom slučaju, ako se želi, jedan do četiri atoma vodonika mogu biti zamenjeni sa Ci-C4-alkil, hidroksi-Ci-C4-alkil, Ci-C4-alkoksi-Ci-C4-alkil, hidroksi-Ci-C4-alkoksi-Ci-C4-alkil, fenil ili benzil, bolje amonijum, dimetilamonijum, diizopropilamonijum, tetrametilamonijum, tetrabutilamonijum, 2-(2-hidroksiet-l-oksi)et-l-il amonijum, di(2—hidroksiet-1-il)amonijum, trimetilbenzilamonijum, pored toga fosofonijum jonima, sulfonijum jonima, radije tri (Ci-C4-alkil) sulfonijum i sulfoksonijum jonima, radije tri (Ci-C4-alkil) sulfoksonijumom. Suitable cations are, in particular, ions of alkali metals, preferably lithium, sodium and potassium, alkaline earth metals, preferably calcium and magnesium, and transition metals, preferably manganese, copper, zinc and iron, and also ammonium, where it is possible in this case, if desired, one to four hydrogen atoms can be replaced by Ci-C4-alkyl, hydroxy-Ci-C4-alkyl, Ci-C4-Alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-Alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyethyl-1-oxy)ethyl-1-yl ammonium, di(2-hydroxyethyl-1-yl)ammonium, trimethylbenzylammonium, in addition phosphonium. ions, sulfonium ions, rather three (Ci-C4-alkyl) sulfonium and sulfoxonium ions, preferably three (Ci-C4-alkyl) sulfoxonium.

Anjoni za pogodne adicione soli sa kiselinama su uglavnom hlorid, bromid, fluorid, hidrogen sulfat, sulfat, dihidrogen fosfat, hidrogen fosfat, nitrat, hidrogen karbonat, karbonat, heksafluorosilikat, heksafluorofosfat, benzoat i anjoni Ci-C4-alkanoičnih kiselina, radije formi jat, acetat, propionat i butirat. Anions for suitable addition salts with acids are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and anions of Ci-C4-alkanoic acids, preferably in the form of jat, acetate, propionate and butyrate.

U specifikaciji i zantevima, izraz 2,4—D označava 2,4— dihloro-sirćetnu kiselinu, 2,4—D može takodje da egzistira u obliku njenih kompatabilnih estara ili soli koji ne zagadjuju životnu sredinu. Pogodne soli su, generalno, soli onih katjona koje koji ne utiču nepovoljno na hebicidno delovanje na aktivne sastojke. In the specification and specifications, the term 2,4-D means 2,4-dichloroacetic acid, 2,4-D can also exist in the form of its compatible esters or salts that do not pollute the environment. Suitable salts are, in general, salts of those cations which do not adversely affect the herbicidal action of the active ingredients.

Odgovarajući katjoni su, osobito, joni alkalnih metala, poželjno litijuma, natrijuma i kalijuma, zemnoalkalnih metala, poželjno kalcijum ili magnezijum, i tranzicioni metali, poželjno mangan, bakar, cink i gvoždje, a takodje i amonijum, pri čemu je moguće u ovom slučaju ako se želi, jedan do četiri atoma vodonika mogu biti zamenjeni sa Ci~C4-alkil, hidroksi-Ci-C4-alkil, Ci-C4-alkoksi-Ci-C4-alkil, hidroksi-Ci-C4-alkoksi-Ci-C4-alkil, fenil ili benzil, poželjno amonijum, dimetilamonijum, diizopropilamonijum, (2-hidroksi-et-l-il)amonijum, di(2-hiđroksi-et-l-il)amonijum ili tri(2-hidroksi-et-l-il)-amonijum. Suitable cations are, in particular, ions of alkali metals, preferably lithium, sodium and potassium, alkaline earth metals, preferably calcium or magnesium, and transition metals, preferably manganese, copper, zinc and iron, and also ammonium, where it is possible in this case, if desired, one to four hydrogen atoms can be replaced by Ci~C4-alkyl, hydroxy-Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-C 1 -C 4 -Alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, (2-hydroxy-eth-1-yl)ammonium, di(2-hydroxy-eth-1-yl)ammonium or tri(2-hydroxy-eth-1-yl)-ammonium.

Izuzetno prikladni katjoni su natrijum, dimetilamonijum, di (2-hidroksi-et-l-il)amonijum i tri (2-hidroksi-et-l-il)-amonijum. Particularly suitable cations are sodium, dimethylammonium, di(2-hydroxy-eth-1-yl)ammonium and tri(2-hydroxy-eth-1-yl)-ammonium.

Prikladni estri 2,4-dihlorofenoksisirćetne kiseline (2,4-D) su Ci-C8_alkil estri, na primer metil, etil, propil, 1-metiletil, butil, 1-metilpropil, 2-metilpropil, 1,1-dimetil-etil, pentil, 1-metilbutil, 2-metilbutil, 3-metilbutil, 2,2-dimetilpropil, 1-etilpropil, heksil, 1, 1-dimetilpropil, 1,2-dimetilpropil, 1-metilpentil, 2-metilpentil, 3-metil-pentil, 4-metilpentil, 1,1-dimetilbutil, 1,2-dimetilbutil, 1,3-dimetilbutil, 2,2-dimetilbutil, 2,3-dimetilbutil, 3,3-dimetilbutil, 1-etilbutil, 2-etilbutil, 1,1,2-trimetil-propil, 1- etil-l-metilpropil, l-etil-3-metilpropil, heptil, 5-metil-l-heksil, oktil, 6-metil-l-heptil, 2-etil-l-heksil ili 4—etil-1-heksil estri, ili Ci-C-j-alkoksi-Ci-C^-alkil estri na primer metoksimetil, etoksimetil, propoksimetil, (1-metiletoksi)metil, butoksimetil, (1-metilpropoksi)metil, (2-metilpropoksi)-metil, (1,1-dimetiletoksi)metil, 2-(metoksi)etil, 2-(etoksi)etil, 2-(propoksi)etil, 2-(l-metiletoksi)etil, 2-(butoksi)etil, 2-(1-metilpropoksi)-etil, 2- (2-metilpropoksi)etil, 2-(1,1-dimetiletoksi ) etil, 2-(metoksi)propil, 2-(etoksi)propil, 2-(propoksi)propil, 2-(l-metiletoksi)propil, 2-(butoksi)propil, 2-(1-metil-propoksi) propil, 2-(2-metilpropoksi)propil, 2-(1,1-dimetil-etoksi ) propil , 3-(metoksi)propil, 3-(etoksi)propil, 3-(propoksi)propil, 3-(1-metiletoksi)propil, 3-(butoksi)propil, 3- (1-metilpropoksi)propil, 3-(2-metil-3-propoksi)propil, 3-(1,1-dimetiletoksi)propil, 2-(metoksi)butil, 2-(etoksi)butil, 2-(propoksi)butil, 2-(1-metiletoksi)butil, 2-(butoksi)butil, 2-(1-metilpropoksi)butil, 2-(2-metilpropoksi)butil, 2-(1,1-dimetiletoksi)butil, 3-(metoksi)butil, 3-(etoksi)butil, 3-(propoksi)butil, 3-(metiletoksi)butil, 3-(butoksi)butil, 3-(l-metilpropoksi)butil, 3-(2-metilpropoksibutil, 3-(1,1-dimetiletoksi)butil, 4-(metoksi)butil, 4-(etoksi)butil, 4-(propoksi)butil, 4-(1-metiletoksi)butil, 4-(butoksi)butil, 4-(1-metilpropoksi)butil, 4-(2-metilpropoksi)butil ili 4—(1,1-dimetiletoksi)butil estri; Suitable esters of 2,4-dichlorophenoxyacetic acid (2,4-D) are C1-C8_alkyl esters, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethyl-ethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1-hexyl. 1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl-pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropyl, 1- ethyl-1-methylpropyl, 1-ethyl-3-methylpropyl, heptyl, 5-methyl-1-hexyl, octyl, 6-methyl-1-heptyl, 2-ethyl-1-hexyl or 4-ethyl-1-hexyl esters, or C 1 -C 1 -alkoxy-C 1 -C 4 -alkyl esters for example methoxymethyl, ethoxymethyl, propoxymethyl, (1-methylethoxy)methyl, butoxymethyl, (1-methylpropoxy)methyl. (2-methylpropoxy)-methyl, (1,1-dimethylethoxy)methyl, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(propoxy)ethyl, 2-(l-methylethoxy)ethyl, 2-(butoxy)ethyl, 2-(1-methylpropoxy)-ethyl, 2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(butoxy)ethyl, 2-(propoxy)propyl, 2-(l-methylethoxy)propyl, 2-(butoxy)propyl, 2-(1-methyl-propoxy) propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethyl-ethoxy ) propyl , 3-(methoxy)propyl, 3-(ethoxy)propyl, 3-(1-methyl-propoxy)propyl, 3-(butoxy)propyl, 3- (1-methylpropoxy)propyl, 3-(2-methyl-3-propoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(butoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(propoxy)butyl, 3-(methylethoxy)butyl, 3-(butoxy)butyl, 3-(l-methylpropoxy)butyl, 3-(2-methylpropoxybutyl, 3-(1,1-dimethylethoxy)butyl, 4-(ethoxy)butyl, 4-(ethoxy)butyl) 4-(1-methylethoxy)butyl, 4-(butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl or 4-(1,1-dimethylethoxy)butyl esters;

Posebno prikladni estri su 1-metil-l-etil, butil, 6-metil-l-heptil, 2-etil-l-heksil ili 2-butoksi-l-etil estri. Particularly suitable esters are 1-methyl-1-ethyl, butyl, 6-methyl-1-heptyl, 2-ethyl-1-hexyl or 2-butoxy-1-ethyl esters.

Primeri ariloksifenoksipropionata kao herbicida koji su prikladni za upotrebu u inventivnim postupcima i smešama su fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, kvizalofop-p-terfuril, kvizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propakvizafop, kvizalafop-etil, kvizalafop-p-etil ili slični, ili jednog od njihovih kompatabilnih soli i estara koji ne zagadjuju životnu sredinu, posebno fenoksaprop-p-etil. Prikladne soli ili estri su slični onima koji su nabrojani za 2,4-D. Examples of aryloxyphenoxypropionate herbicides suitable for use in the inventive methods and compositions are fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, quizalofop-p-terfuryl, quizalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop-butyl, fenthioprop, propaquizafop, quizalafop-ethyl, quizalafop-p-ethyl or the like, or one of their compatible, non-polluting salts and esters, especially fenoxaprop-p-ethyl. Suitable salts or esters are similar to those listed for 2,4-D.

U specifikaciji i zahtevima, izraz alkil (sam ili u kombinaciji) predstavlja C].-C6-alkil grupu, posebno Ci-C4-alkil grupa; izraz alkoksi (sam ili u kombinaciji) predstavlja Ci-C6-alkoksi grupu, posebno Ci-C4-alkoksi grupu; izraz alkenil (sam ili u kombinaciji) predstavlja C3-C6-alkenil grupu, posebno C3-C4-alkenil grupu; izraz alkinil predstavlja C3-C6-alkinil grupu, posebno C3-C4-alkinil grupu. In the specification and claims, the term alkyl (alone or in combination) means a C1-C6-alkyl group, especially a C1-C4-alkyl group; the term alkoxy (alone or in combination) represents a C 1 -C 6 -alkyl group, in particular a C 1 -C 4 -alkyl group; the term alkenyl (alone or in combination) represents a C3-C6-alkenyl group, especially a C3-C4-alkenyl group; the term alkynyl represents a C3-C6-alkynyl group, especially a C3-C4-alkynyl group.

Sinergetske kombinacije koje imaju prednost prema ovom pronalasku su one kombinacije sa dva ili tri herbicida koje sadrže ariloksipikolinamid formule I gde Synergistic combinations that are preferred according to the present invention are those combinations with two or three herbicides containing an aryloxypicolinamide of formula I wherein

Z je kiseonik; Z is oxygen;

Ri je vodonik; R 1 is hydrogen;

<q>je 0; <q>is 0;

R3je.vodonik; R3 is hydrogen;

X je haloalkil; i X is haloalkyl; and

Y je vodonik ili fluor. Y is hydrogen or fluorine.

Posebne su one kombinacije sa dva herbicida ili tri herbricida koje sadrže ariloksipikolinamid formule I gde n=l, a X je vezano u meta-položaju za fenil radikal (u odnosu na kiseonični most). Special are those combinations with two herbicides or three herbicides that contain aryloxypicolinamide of formula I where n=1, and X is attached in the meta-position to the phenyl radical (relative to the oxygen bridge).

Pogodnije sineregetske kombinacije sa dva herbicida i tri herbicida su one gde jedinjenje formule I je N-(4-fluorofenil)-6-[3-trifluorometil)fenoksi]-2-piridin karboksamid predstavljen formulom niže, a u nastavku označen kao pikolinafen More suitable two-herbicide and three-herbicide synergetic combinations are those where the compound of formula I is N-(4-fluorophenyl)-6-[3-trifluoromethyl)phenoxy]-2-pyridine carboxamide represented by the formula below, hereinafter designated as picolinafen

Sledeće pogodno ostvarenje prema ovom pronalasku su one kombinacije sa dva herbicida u kojima drugi herbicid je ariloksifenoksipropionat herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom. A further preferred embodiment of the present invention is those combinations with two herbicides in which the second herbicide is an aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop-butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters.

Kao sledeće pogodno ostvarenje prema ovom pronalasku su one kombinacije sa dva herbicida gde drugi herbicid je ariloksi-fenoksipropionat kao herbicid. Posebno, drugi herbicid je fenoksaprop-p-etil. As a further preferred embodiment according to the present invention are those combinations with two herbicides where the second herbicide is aryloxy-phenoxypropionate as the herbicide. In particular, another herbicide is fenoxaprop-p-ethyl.

Kao sledeće pogodno ostvarenje prema ovom pronalasku su one kombinacije sa tri herbicida gde je drugi herbicid ariloksi-fenoksipropionat. Naročito, drugi herbicid je fenoksaprop-p-etil. As a further preferred embodiment according to the present invention are those combinations with three herbicides where the second herbicide is aryloxy-phenoxypropionate. In particular, another herbicide is fenoxaprop-p-ethyl.

U savremenoj praksi, kombinacija prema ovom pronalasku se može aplicirati simultano (kao tank mix ili premix), separatno ili sekvencijalno. In modern practice, the combination according to this invention can be applied simultaneously (as tank mix or premix), separately or sequentially.

Tako, prema postupku iz ovog pronalaska sinergetski efikasna količina kombinacije sa dva herbicida ariloksipikolinamida i drugog herbicida odabranog od ariloksifenoksipropionat herbicida koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom; ili sinergetski efikasna količina kombinacije sa tri herbicida ariloksipikolinamida, drugog herbicida koji je ariloksifenoksipropionska kiselina - herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom i trećeg herbicida koji je 2,4-D ili jedan od njenih kompatabilnih estara ili soli, primenjena je na mestima na kojima rastu neželjene biljke, na lišće ili korene neželjenih biljaka, posebno na biljke .odabrane od vrsta Polvgonum, Kochia, Galeopsis, Galium, Stelaria, Sinapis, i Avena, opciono u prisustvu useva, poželjno žitnih useva kao što je pšenica, ječam, pirinač, kukuruz, raž i slični drugi. Thus, according to the method of the present invention, a synergistically effective amount of a combination with two herbicides of aryloxypicolinamide and another herbicide selected from aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop-butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters; or a synergistically effective amount of a three-herbicide combination of aryloxypicolinamide, another herbicide that is aryloxyphenoxypropionic acid - a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters and a third herbicide which is 2,4-D or one of its compatible esters or salts, was applied to the sites where the unwanted plants grow, to the leaves or roots of the unwanted plants, especially to plants selected from Polvgonum, Kochia, Galeopsis, Galium, Stelaria, Sinapis, and Avena species, optionally in the presence crops, preferably cereal crops such as which is wheat, barley, rice, corn, rye and similar others.

Sinergetski efikasna količina za kombinacije sa dva i tri herbicida se može menjati u zavisnosti od postojećih stanja kao što je specifičnost prisutne druge i treće komponente, obima zakorovljenosti, uskladjenost vremena primene, vre-menskih prilika, stanja zemljišta, načina primene, topo-grafskih karakteristika, ciljne vrste useva i sličnih drugih stanj a. The synergistically effective amount for combinations with two and three herbicides can be changed depending on the existing conditions such as the specificity of the second and third components present, the extent of weediness, the timing of application, weather conditions, soil conditions, method of application, topographical characteristics, target crop type and similar other conditions.

Kombinacije koje imaju prednost sa dva herbicida prema ovom pronalasku su one u kojima odnos težina/težina za ariloksi-pikolinamid formule I prema drugom jedinjenju je oko: ariloksipikolinamid:ariloksifenoksipropionat herbicid 1:1 do 1:10. Preferred two-herbicide combinations of the present invention are those in which the weight/weight ratio of the aryloxy-picolinamide of formula I to the second compound is about: aryloxypicolinamide:aryloxyphenoxypropionate herbicide 1:1 to 1:10.

Pogodnije kombinacije sa dva herbicida su one u kojima odnos težina/težina pikolinafena prema drugoj komponenti je oko: More suitable combinations with two herbicides are those in which the weight/weight ratio of picolinafen to the other component is about:

pikolinafen:fenoksaprop-p-etil, 1:1 do 1:10. picolinafen:fenoxaprop-p-ethyl, 1:1 to 1:10.

Pogodne kombinacije sa tri herbicida prema ovom pronalasku su one u kojima odnos težina/težina za ariloksipikolinamid formule I prema drugoj komponenti (obliku soli ili estara) prema trećoj komponenti je oko: ariloksipikolinamid: ariloksifenoksipropionat herbicidu : 2,4-D (ili u obliku soli ili estara), 1:1:1 do 1:25:10. Suitable three-herbicide combinations according to this invention are those in which the weight/weight ratio for aryloxypicolinamide of formula I to the second component (salt or ester form) to the third component is about: aryloxypicolinamide: aryloxyphenoxypropionate herbicide : 2,4-D (either in salt or ester form), 1:1:1 to 1:25:10.

Pogodnije kombinacije sa tri herbicida prema ovom pronalasku su one u kojim težina/težina odnos za pikolinafen prema drugoj komponenti prema trećoj komponenti je oko: Pikolinafen : fenoksaprop-p-etil : 2,4—D, 1:1:1 do 1:25:10. More suitable combinations with three herbicides according to this invention are those in which the weight/weight ratio for picolinafen to the second component to the third component is about: Picolinafen : fenoxaprop-p-ethyl : 2,4-D, 1:1:1 to 1:25:10.

Ovaj pronalazak takodje obezbedjuje sinergetsku herbicidnu smešu koja sadrži prihvatljiv nosač za poljoprivrene svrhe i sinergetski efikasnu količinu kombinacije sa dva herbicida za ariloksipikolinamid formule I i drugo herbicidno jedinjenje odabrano od ariloksifenoksipropionat herbicida koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom. Ovaj pronalazak dalje obezbedjuje sinergetski herbicidnu smešu koja sadrži poljoprivredno prihvatljiv nosač i sinergetski efikasnu količnu kombinacije od tri herbicida i to ariloksipikolinamid jedinjenja formule I, drugiog herbicida koji je ariloksifenoksipropionska kiselina - herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom i trećeg herbicida koji je 2,4-D ili jedan od njenih kompatabilnih estara ili soli. The present invention also provides a synergistic herbicidal composition comprising an agriculturally acceptable carrier and a synergistically effective amount of a combination of two aryloxypicolinamide herbicides of formula I and a second herbicidal compound selected from an aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, phenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters. The present invention further provides a synergistic herbicidal mixture containing an agriculturally acceptable carrier and a synergistically effective amount of a combination of three herbicides namely an aryloxypicolinamide compound of formula I, the second herbicide being an aryloxyphenoxypropionic acid - a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, phenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters and a third herbicide which is 2,4-D or one of its compatible esters or salts.

Poljoprivredno prihvatljiv nosač može biti čvrst ili tečan, poželjno tečan, još bolje voda. Bez obzira što se ne zahteva, kombinacija smeša prema ovom pronalasku mogu takodje An agriculturally acceptable carrier can be solid or liquid, preferably liquid, even better water. Although not required, the combination of mixtures according to this invention may also

da sadrže druge aditive kao što su djubriva, inertna pomoćna sredsta za formulaciju, naime, površinski aktivna sredstva, emulgatore, sredstva za sprečavanje stvaranja pene, boje, punioce ili bilo koji od uobičajenih inertnih sastojaka koji se tipično upotrebljavaju za formulaciju herbicidni proizvoda. to contain other additives such as fertilizers, inert formulation aids, namely, surfactants, emulsifiers, antifoam agents, colors, fillers or any of the usual inert ingredients typically used in the formulation of herbicidal products.

Smeše prema ovom pronalasku se mogu formulisati u bilo kome uobičajenom obliku, na primer u obliku udvojenog pakova-nja, ili u obliku vodenog koncentrat, rastvorijivih granula, disperzionih granula ili u sličnim oblicima. The compositions according to the present invention can be formulated in any conventional form, for example in the form of a double package, or in the form of an aqueous concentrate, soluble granules, dispersion granules or in similar forms.

Pogodne smeše u kombinaciji sa dva herbicida su one smeše Suitable mixtures in combination with the two herbicides are those mixtures

u kojima ariloksipikolinamidno jedinjenje je pikolinafen. wherein the aryloxypicolinamide compound is picolinaphene.

Takodje pogodne su one sinergetske smeše u kombinaciji sa dva herbicida koje sadrže drugi herbicid odabran od ariloksifenoksipropionat herbicida koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom. Pogodnije smeše sa dva herbicida prema ovom pronalasku su one smeše prema ovom pronalasku gde odnos težina/težina pikolina prema drugoj komponenti je oko: Also suitable are those synergistic mixtures in combination with two herbicides that contain another herbicide selected from aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hizalafop-ethyl and hizalafop-p-ethyl or one of its environmentally compatible salts or esters. More suitable two-herbicide mixtures of the present invention are those mixtures of the present invention where the weight/weight ratio of picoline to the second component is about:

pikolinafen:fenoksaprop-p-etil, 1:1 do 1:10. picolinafen:fenoxaprop-p-ethyl, 1:1 to 1:10.

Pogodne smeše kombinacije sa tri herbicida prema ovom pronalasku su one smeše u kojima pikolinamidno jedinjenje je pikolinafen. Takodje pogodne su one sinergetske smeše u kombinaciji sa tri herbicida pri čemu treći herbicid je 2,4-D ili jedan od njenih kompatabilnih estara ili soli. Pogodnije smeše sa kombinacijom od tri herbicida prema ovom pronalasku su one smeše u kojima odnos težina/težina pikolinafena prema drugoj komponenti prema trećoj komponenti je oko: pikolinafen:fenoksaprop-p-etil:2,4—D, 1:1:1 do 1:25:10. Suitable tri-herbicide combination mixtures according to the present invention are those mixtures in which the picolinamide compound is picolinaphene. Also suitable are those synergistic mixtures in combination with three herbicides, where the third herbicide is 2,4-D or one of its compatible esters or salts. More suitable three-herbicide combination mixtures according to the present invention are those mixtures in which the weight/weight ratio of picolinafen to the second component to the third component is about: picolinafen:fenoxaprop-p-ethyl:2,4-D, 1:1:1 to 1:25:10.

Radi boljeg razumevanja ovog pronalaska, dati su specifični primeri koji slede. Ovi primeri su samo ilustrativni i ne treba ih shvatiti kao ograničenje delokruga i nepoštovanje savremenih principa prema pronalasku na bilo koji način. For a better understanding of the present invention, the following specific examples are provided. These examples are illustrative only and should not be construed as limiting the scope and disrespecting the current principles of the invention in any way.

U primarima koji slede, sinergizam za kombinacije sa dva herbbicida odredjen je po Colby metodi (S.R. Colby, Weeds 1967 (15), 20), naime, očekivani (ili predvidjajući) odgovor za kombinaciju je izračunat uzimanjem proizvoda za vidljiv odgovor za svaku pojedinačnu komponentu iz kombinacije kada je aplicirana sama deljenjem sa 100 i oduzimanjem ive vrednosti od zbira vidljivog odgovora sa svaku komponentu kada je sama aplicirana. Sinergizam kombinacije se zatim odredjuje poredjenjem vidljivog odgovora za kombinaciju sa očekivanim (ili predvidjajućem) odgovora tako izračunato od vidljivih odgovora za svaku pojedinačnu samu komponentu. Ako je vidljiv odgovor za kombinaciju veći od očekivanog (ili predviđajućeg) odgovora tada je kombinacija rečeno da će biti sinergetska i spada unutar definicije za sinergetski efekat kao što je prethodno definisano. In the primers that follow, synergism for combinations with two herbicides was determined by the Colby method (S.R. Colby, Weeds 1967 (15), 20), namely, the expected (or predicted) response for the combination was calculated by taking the product of the visible response for each individual component of the combination when applied alone, dividing by 100 and subtracting the ive value from the sum of the visible response with each component when applied alone. Synergism of the combination is then determined by comparing the observed response for the combination with the expected (or predicted) response as calculated from the observed responses for each individual component alone. If the observed response for a combination is greater than the expected (or predicted) response then the combination is said to be synergistic and falls within the definition for a synergistic effect as previously defined.

Gore pomenuto je ilustrovano matematičkim putem koji sledi, pri čemu kombinacija sa dva herbicida, C2, je sastavljena od komponente X plus komponente Y, a vid. označava vidljiv odgovor za kombinaciju C2. The above-mentioned is illustrated by the following mathematical way, whereby the combination with two herbicides, C2, is composed of component X plus component Y, and vid. indicates the visible answer for combination C2.

Na sličan način u slučaju kombinacije sa tri herbicida, G3,je sastavljena od komponente X plus komponente I plus komponente Z, a vid. označava očekivani odgovor za kombinaciju C3. Similarly, in the case of the combination with three herbicides, G3 is composed of component X plus component I plus component Z, and vid. indicates the expected response for combination C3.

U primerima koji slede, tolerantnost useva je procenjivana periodično tokom sezone rasta. Prvo procena ge uzeta jedne ili dve nedelje posle tretiranja i krajnja procena je izvršena upravo pre žetve. Za sva tretiranja opisana u primerima koji slede toleratnost useva je komercijalno prihvatljiva, naime, 20% oštećenja, na svakih tri testiranih useva. Bez tretiranja rezultati ukazuju na komercijalno neprihvatljivo oštećenje ječma, tvrde pšenice ili crvene tvrdog zrna jare pšenice. In the examples that follow, crop tolerance is evaluated periodically during the growing season. The first evaluation of ge was taken one or two weeks after treatment and the final evaluation was performed just before harvest. For all treatments described in the examples that follow, crop tolerance is commercially acceptable, namely 20% damage, for every three crops tested. Without treatment, the results indicate commercially unacceptable damage to barley, durum wheat or red durum spring wheat.

PRIMER 1 EXAMPLE 1

Ocena herbicidne aktivnosti kombinacije pikolinafena i fenoksaprop-p-etila Evaluation of the herbicidal activity of the combination of picolinafen and fenoxaprop-p-ethyl

Sledeći u suštini istu proceduru koja je opisana u primeru 1 i upotrebljavajući pikolinafen i fenoksaprop-p-etil, dobijeni podaci su prikazani u tablici I. Following essentially the same procedure as described in Example 1 and using picolinafen and fenoxaprop-p-ethyl, the data obtained are shown in Table I.

Kao što se može videti od podataka prikazanih u tablici As can be seen from the data shown in the table

I, primena kombinacije pikolinafena plus fenoksaprop-p-etila daje značajno veću kontrolu korova od one koja je predvidjena pri kontroli korova i koja rezultuje pri primeni ili pikoliafena samog ili fenoksaprop-p-etila samog. And, the application of the combination of picolinafen plus fenoxaprop-p-ethyl provides significantly greater weed control than that predicted by weed control that results from the application of either picoliafen alone or fenoxaprop-p-ethyl alone.

PRIMER 2 EXAMPLE 2

Ocena herbicidne aktivnosti kombinacije pikolinafena, fenoksaprop-p-etila i 2,4—D Evaluation of the herbicidal activity of the combination of picolinafen, fenoxaprop-p-ethyl and 2,4-D

Sledeći u suštini istu proceduru opisanu u primeru 1 i upotrebljavajući pikolinafen, fenoksaprop-p-etil i 2,4—D, dobijeni podaci su prikazani u tablici II. Following essentially the same procedure described in Example 1 and using picolinafen, fenoxaprop-p-ethyl and 2,4-D, the data obtained are shown in Table II.

Kao što se može videti od podataka u tablici II, primena kombinacije pikolinafena, fenoksaprop-p-etila i 2,4—D daje značajno veću kontrolu korova od one koja je predvidjena pri kontroli korova koja rezultuje pri primeni pikolinafena samog, ili fenoksaprop-p-etila samog ili 2,4—D same. As can be seen from the data in Table II, application of the combination of picolinafen, fenoxaprop-p-ethyl, and 2,4-D provides significantly greater weed control than that predicted by weed control resulting from the application of picolinafen alone, or fenoxaprop-p-ethyl alone, or 2,4-D alone.

Claims (11)

1. Sinergetska herbicidna kompozicija naznačena time što sadrži poljoprivredno prihvatljiv nosač i sinergetski efikasnu količinu smeše dva herbicida, kombinaciju ariloksipikolinamida formule I gde Z predstavlja kiseonik ili atom sumpora; Ripredstavlja vodonik ili atom halogena ili alkil ili haloalkil grupu; R2predstavlja vodonik ili alkil grupu; q je 0 ili 1; R3predstavlja vodonik ili alkil ili alkenil grupu; ili svaka grupa X nezavisno predstavlja atom halogena ili opciono supstituisanu alkil ili alkoksi grupu, poželjno haloalkil grupu, ili alkeniloksi, cijano, karboksi, alkoksikarbonil, (alkiltio)karbonil, alkilkarbonil, amido, alkilamido, nitro, alkiltio, haloalkiltio, alkeniltio, alkiniltio, alkil-sulfinil, alkilsulfonil, alkiloksiaminoalkil ili alkeniloks-iminoalkil grupu; n je 0 ili ceo broj od 1 do 5; ili svaka grupa Y nezavisno predstavlja atom halogena ili alkil, nitro, cijano, haloalkil, alkoksi ili haloalkoksi grupu; i m je 0 ili ceo broj od 1 do 5 ili jednu od kompatibilnih soli jedinjenja formule I koje ne zagađuju životnu sredinu; i drugi herbicid koji je ariloksifenoksipropionat herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom.1. A synergistic herbicidal composition characterized by containing an agriculturally acceptable carrier and a synergistically effective amount of a mixture of two herbicides, a combination of aryloxypicolinamide of formula I where Z represents oxygen or a sulfur atom; Represents hydrogen or a halogen atom or an alkyl or haloalkyl group; R2 represents hydrogen or an alkyl group; q is 0 or 1; R3 represents hydrogen or an alkyl or alkenyl group; or each group X independently represents a halogen atom or an optionally substituted alkyl or alkoxy group, preferably a haloalkyl group, or an alkenyloxy, cyano, carboxy, alkoxycarbonyl, (alkylthio)carbonyl, alkylcarbonyl, amido, alkylamido, nitro, alkylthio, haloalkylthio, alkenylthio, alkynylthio, alkylsulfinyl, alkylsulfonyl, alkyloxyaminoalkyl or alkenyloxyiminoalkyl group; n is 0 or an integer from 1 to 5; or each group Y independently represents a halogen atom or an alkyl, nitro, cyano, haloalkyl, alkoxy or haloalkoxy group; and m is 0 or an integer from 1 to 5 or one of the compatible salts of compounds of formula I which do not pollute the environment; and another herbicide which is an aryloxyphenoxypropionate herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hyzalofop-ethyl and hyzalofop-p-ethyl or one thereof salts or esters compatible with the environment. 2. Kompozicija prema zahtevu 1, naznačena time što sadrži ariloksipikolinamid formule I gde Z je kiseonik; Ri je vodonik; <q>je 0; R3je vodonik; X je haloalkil; i Y je vodonik ili fluor.2. The composition according to claim 1, characterized in that it contains an aryloxypicolinamide of formula I where Z is oxygen; Ri is hydrogen; <q> is 0; R 3 is hydrogen; X is haloalkyl; and Y is hydrogen or fluorine. 3. Kompozicija prema zahtevu 2, naznačena time što pomenute formule I ariloksipikolinamid je pikolinafen.3. Composition according to claim 2, characterized in that said formula I aryloxypicolinamide is picolinafen. 4. Kompozicija prema zahtevu 1, naznačena time što drugi herbicid je fenoksaprop-p-etil.4. The composition according to claim 1, characterized in that the second herbicide is fenoxaprop-p-ethyl. 5. Kompozicija prema zahtevu 4, naznačena time što pomenute formule I ariloksipikolinamid je pikolinafen.5. Composition according to claim 4, characterized in that said formula I aryloxypicolinamide is picolinaphene. 6. Sinergetska herbicidna kompozicija naznačena time što sadrži poljoprivredno prihvatljiv nosač i sinergetski efikasnu količinu tri herbicida koja se u suštini sastoji od: ariloksipikolinamida formule I gde Z predstavlja kiseonik ili atom sumpora; Ripredstavlja vodonik ili atom halogena ili alkil ili haloalkil grupu; R2predstavlja vodonik ili alkil grupu; q je 0 ili 1 R3predstavlja vodonik ili alkil ili alkenil grupu; ili svaka grupa X nezavisno predstavlja atom halogena ili opciono supstituisanu alkil ili alkoksi grupu, poželjno haloalkil grupu, ili alkeniloksi, cijano, karboksi, alkoksikarbonil, (alkiltio)karbonil, alkilkarbonil, amido, alkilamido, nitro, alkiltio, haloalkiltio, alkeniltio, alkiniltio, alkil-sulfinil, alkilsulfonil, alkiloksiiminoalkil ili alkeniloksi-iminoalkil grupu; n je 0 ili ceo broj od 1 do 5; ili svaka grupa Y hezavisno predstavlja atom halogena ili alkil, nitro, cijano, haloalkil, alkoksi ili haloalkoksi grupu; i m je 0 ili ceo broj od 1 do 5 ili jednu od kompatabilnih soli jedinjenja formule I koje ne zagađuju životnu sredinu; drugi herbicid koji je ariloksifenoksipropionska kiselina - herbicid koji je izabran iz grupe koju čine fluazifop-p-butil, fenoksaprop-etil, fenoksaprop-p-etil, hizalofop-p-terfuril, hizalofop-p, haloksifop-metil, klodinafop-propargil, izoksapurifop, cihalofop butil, fentioprop, propahizafop, hizalafop-etil i hizalafop-p-etil ili jedna od njegovih soli ili estara kompatibilnih sa životinom sredinom i treći herbicid koji je 2,4-D ili jedan od njenih kompatabilnih estara ili soli.6. A synergistic herbicidal composition characterized in that it contains an agriculturally acceptable carrier and a synergistically effective amount of three herbicides consisting essentially of: aryloxypicolinamide of formula I where Z represents oxygen or a sulfur atom; Represents hydrogen or a halogen atom or an alkyl or haloalkyl group; R2 is hydrogen or an alkyl group; q is 0 or 1 R3 represents hydrogen or an alkyl or alkenyl group; or each group X independently represents a halogen atom or an optionally substituted alkyl or alkoxy group, preferably a haloalkyl group, or an alkenyloxy, cyano, carboxy, alkoxycarbonyl, (alkylthio)carbonyl, alkylcarbonyl, amido, alkylamido, nitro, alkylthio, haloalkylthio, alkenylthio, alkynylthio, alkylsulfinyl, alkylsulfonyl, alkyloxyiminoalkyl or alkenyloxyiminoalkyl group; n is 0 or an integer from 1 to 5; or each group Y is optionally a halogen atom or an alkyl, nitro, cyano, haloalkyl, alkoxy or haloalkyl group; and m is 0 or an integer from 1 to 5 or one of the compatible salts of the compound of formula I which do not pollute the environment; another herbicide that is aryloxyphenoxypropionic acid - a herbicide selected from the group consisting of fluazifop-p-butyl, fenoxaprop-ethyl, fenoxaprop-p-ethyl, hyzalofop-p-terfuryl, hyzalofop-p, haloxyfop-methyl, clodinafop-propargyl, isoxapurifop, cyhalofop butyl, fenthioprop, propahizafop, hyzalofop-ethyl and hyzalofop-p-ethyl or one of its environmentally compatible salts or esters and a third herbicide which is 2,4-D or one of its compatible esters or salts. 7. Kompozicija prema zahtevu 6, naznačena time što sadrži ariloksi pikolinamid formule I gde Z je kiseonik; Ri je vodonik; <q>je 0; R3je vodonik; X je haloalkil; i Y je vodonik ili fluor.7. The composition according to claim 6, characterized in that it contains an aryloxy picolinamide of formula I where Z is oxygen; Ri is hydrogen; <q> is 0; R 3 is hydrogen; X is haloalkyl; and Y is hydrogen or fluorine. 8. Kompozicija prema zahtevu 7, naznačena time što je pomenuti ariloksipikolin-amid formule I pikolinafen.8. Composition according to claim 7, characterized in that said aryloxypicolin-amide of formula I is picolinaphene. 9. Kompozicija prema zahtevu 6, naznačena time što je drugi herbicid fenoksa-prop-p-etil.9. The composition according to claim 6, characterized in that the second herbicide is phenoxa-prop-p-ethyl. 10. Kompozicija prema zahtevu 9, naznačena time što je pomenuti ariloksi-pikolinamid formule I pikolinafen.10. Composition according to claim 9, characterized in that said aryloxy-picolinamide of formula I is picolinaphene. 11. Postupak za sinergetsku kontrolu neželjenih biljaka, naznačen time što obuhvata primenu na mestima na kojima rastu pomenute biljke ili tretiranje lišća ili korena pomenutih biljaka sinergetsko efikasnom količinom kompozicija koje su zaštićene u bilo kom od zahteva 1 do 10.11. A method for the synergistic control of unwanted plants, characterized by the fact that it includes application to the places where said plants grow or treating the leaves or roots of said plants with a synergistically effective amount of the compositions that are protected in any of claims 1 to 10.
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